Evaluation of Alternate Water

Gas Shift Configurations for

IGCC Systems
August 5, 2009

DOE/NETL-401/080509
 Disclaimer
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Evaluation of Alternate Water Gas Shift Configurations
for IGCC Systems

August 5, 2009

Prepared by:

Eric Grol, NETL

Wen-Ching Yang, Research and Development Solutions, LLC (SAIC)

NETL Contact:

Eric Grol
Office of Systems, Analyses and Planning
412-386-5463

National Energy Technology Laboratory

www.netl.doe.gov
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 Table of Contents
1  Executive Summary .................................................................................................. 1 
2  Background ............................................................................................................... 2 
3  Conclusions and Recommendations ........................................................................ 3 
3.1  Conclusions ......................................................................................................... 3 
3.2  Recommendations ............................................................................................... 8 
4  Base IGCC Case ........................................................................................................ 9 
4.1  Plant Description ................................................................................................. 9 
4.2  Plant Financial Description ............................................................................... 10 
4.3  Base Case WGS Configuration......................................................................... 13 
5  Alternate Sour WGS Configurations .................................................................... 14 
5.1  Case 1 - Single Shift Stage, S:DG = 0.3 ........................................................... 15 
5.2  Case 2 - Single Shift Stage, S:DG = 0.25 ......................................................... 16 
5.3  Case 3 - Two Shift Stages, S:DG = 0.3 ............................................................ 17 
5.4  Case 4 - Two Shift Stages, S:DG = 0.25 .......................................................... 19 
6  Shift Reactor Design Considerations .................................................................... 20 
6.1  Steam-to-Dry Gas Ratio .................................................................................... 20 
6.2  Water Gas Shift Reactor Pressure Drop............................................................ 21 
7  Water Gas Shift Background................................................................................. 22 
7.1  Steam Consumption .......................................................................................... 22 
7.2  Sweet Versus Sour Shift ................................................................................... 23 
7.2.1  Sweet Shift .................................................................................................... 23 
7.2.2  Sour Shift ...................................................................................................... 24 
7.3  WGS Reaction Equilibrium and Stage Operation ............................................ 24 
7.4  WGS Reaction Kinetics .................................................................................... 25 
8  References ................................................................................................................ 27 
1 Executive Summary
As carbon control in Integrated Gasification Combined Cycle (IGCC) systems gains increasing
awareness, emphasis is placed on optimization of the water-gas shift (WGS) reaction. This
process step is required to convert carbon to a form (CO2) that can be separated from coal-
derived syngas by a conventional acid gas removal system. The extent to which CO is converted
to CO2 is determined by the degree of carbon capture required. This analysis considers a range
of carbon capture goals (60-90%) and evaluates several WGS configurations and steam
consumption scenarios that could potentially accommodate each capture target, while realizing
cost and efficiency benefits.

In order to drive the reaction equilibrium toward the water gas shift products (H2 and CO2),
steam is typically introduced at the inlet of the shift reactor. This shift steam is taken from an
intermediate extraction point in the steam turbine. Any steam extracted for the shift is not
expanded in the turbine to produce power, therefore the water gas shift step is typically viewed
as a burden on the steam cycle.

This analysis considers the technical and economic implications of reductions in shift steam
consumption. This reduction will improve steam cycle performance (and system efficiency) by
allowing for the expansion of a greater mass of steam through the turbine. However it will also
result in larger water gas shift reactors to achieve the same level of CO conversion, increasing
capital costs. The tradeoff between improved efficiency and higher capital cost is the focus of
this study.

This study finds that although capital costs increase due to larger reactor volume, the savings in
shift steam is more than adequate to offset this loss. For all cases considered (with the exception
of 90% carbon capture), a shift steam reduction resulted in cost and efficiency improvements.
However 90% carbon capture is only possible by feeding high levels of shift steam, to drive the
reaction equilibrium toward the products. A lower limit does exist with respect to the minimum
amount of shift steam required. If shift steam levels are too low, the required reactor volume
becomes prohibitively large, therefore negating the benefit of steam savings.

1
2 Background
As carbon control in IGCC systems gains increasing awareness, emphasis is placed on
optimization of the water gas shift (WGS) reaction. The WGS reaction converts CO to CO2,
consuming one mole of steam and producing one mole of hydrogen in the process:

H2O + CO ↔ H2 + CO2 ΔHrxn298K = -17,697 Btu/lb-mol (1)

This process step is required to convert carbon to a form (CO2) that can be separated from coal-
derived syngas by a conventional acid gas removal system. The extent to which CO is converted
to CO2 is determined by the degree of carbon capture required. This analyses considers a range
(60-90%) of carbon capturei goals and evaluates several WGS configurations and steam-to-dry
gas (S:DG) molar ratios that could potentially accommodate each capture target, while realizing
cost and efficiency benefits. The study was inspired by a presentation at the 2006 Gasification
Technologies Council Annual Meeting by Rao, Verma, and Cortez that evaluated a bypass water
gas shift configuration for petroleum coke gasification units with co-production of 99% purity
H2, employing an E-Gas gasifier1.

Previous studies2 have shown that a conventional two-stage sour gas shift is capable of
converting approximately 96% of CO initially in the syngas. A dual-stage Selexol unit that
separates incoming CO2 satisfies the 90% carbon capture requirement for that particular study.
For systems that require less than 90% carbon capture, a reduced amount of CO can be shifted,
or the Selexol unit can be downsized to capture less CO2. The former can be done by bypassing
a portion of the raw syngas around the WGS section or by using less shift steam, and the latter by
reducing column size, circulating less solvent, or bypassing a portion of syngas around the
Selexol unit. This analysis maintains the same high performance dual-stage Selexol unit from
the reference study2, and focuses strictly on methods to achieve lower degrees of CO shift by a
combination of steam reduction, and syngas bypass around the shift reactors.

i
For this study, carbon capture is defined as carbon in the coal minus carbon leaving the stack. Any carbon that
exits with the gasifier slag is not considered.

2
3 Conclusions and Recommendations
3.1 Conclusions

The performance results for all cases considered are summarized in Table 1. The significant
differences between cases are the number of shift stages used (one and two reactor
configurations were considered) and the steam-to-dry-gas (S:DG) ratio assumed, which
determines how much shift steam is required (both 0.3 and 0.25 S:DG ratios were evaluated).
If shift steam levels are too low, the required reactor volume becomes prohibitively large,
therefore negating the benefit of the steam savings.

Table 1 - Water Gas Shift Case Results

Case 1 Case 2 Case 3 Case 4
90% C Capture
• Number of stages - - 2 -
• S:DGii - - 0.3 -
• LCOE, ¢/kWh - - 10.32 -
• System Efficiency, % - - 32.4 -
• Bypass, % - - 0 -
• Shift Steam, lb/hr - - 237,931 -
85% C Capture
• Number of stages - - 2 2
• S:DGii - - 0.3 0.25
• LCOE, ¢/kWh - - 10.17 10.10
• System Efficiency, % - - 32.9 33.2
• Bypass, % - - 8 7
• Shift Steam, lb/hr - - 216,575 163,952
80% C Capture
• Number of stages - - 2 2
• S:DGii - - 0.3 0.25
• LCOE, ¢/kWh - - 10.10 10.04
• System Efficiency, % - - 33.2 33.5
• Bypass, % - - 16 15
• Shift Steam, lb/hr - - 196,698 148,318
75% C Capture
• Number of stages 1 1 2 2
• S:DGii 0.3 0.25 0.3 0.25
• LCOE, ¢/kWh 10.05 9.97 10.01 9.97
• System Efficiency, % 33.3 33.6 33.5 33.7
• Bypass, % 6 2 24 23
• Shift Steam, lb/hr 145,751 90,382 175,981 132,782

ii
Steam to dry gas ratio is measured on a molar basis, at the outlet of the last shift reactor.

3
 70% C Capture
• Number of stages 1 1 2 2
• S:DGii 0.3 0.25 0.3 0.25
• LCOE, ¢/kWh 9.96 9.90 9.94 9.90
• System Efficiency, % 33.6 33.9 33.8 34.0
• Bypass, % 16 13 33 32
• Shift Steam, lb/hr 129,672 80,138 155,834 117,009
65% C Capture
• Number of stages 1 1 2 2
• S:DGii 0.3 0.25 0.3 0.25
• LCOE, ¢/kWh 9.87 9.81 9.85 9.82
• System Efficiency, % 33.9 34.2 34.1 34.3
• Bypass, % 26 23 41 40
• Shift Steam, lb/hr 113,308 69,753 135,506 102,190
60% C Capture
• Number of stages 1 1 2 2
• S:DGii 0.3 0.25 0.3 0.25
• LCOE, ¢/kWh 9.78 9.74 9.78 9.75
• System Efficiency, % 34.3 34.5 34.4 34.5
• Bypass, % 37 34 49 48
• Shift Steam, lb/hr 96,341 60,007 116,089 88,067

Summaries of the efficiency and cost results for all cases are shown in Figure 1 and
Figure 2, respectively. The results indicate that in general, there are efficiency and cost
benefits when less shift steam is used (S:DG ratio of 0.25). For carbon capture below
75%, Figure 1 and Figure 2 indicate that the optimum configuration from an efficiency
perspective uses two-stages and a steam-to-dry-gas ratio of 0.25. From a cost point of
view, there is almost no difference if one or two shift stages are used for carbon capture
below 75%, for the 0.25 S:DG cases. This result is counterintuitive, since there are two
shift reactors (instead of one), but will be explained in more detail in later sections. Also
of importance in Figure 1 and Figure 2 is that the maximum carbon capture possible with
one shift reactor is 75%. The only configuration capable of meeting 90% carbon capture
is two shift stages and a S:DG ratio of 0.3.

4
Figure 1 - Water Gas Shift Case Efficiency Results

5
 Figure 2 - Water Gas Shift Case Economic Results

The following conclusions can be drawn from the results shown in Table 1, Figure 1, and
Figure 2:
• For carbon capture greater than 75%, two water gas shift reactors are required.
There is inadequate conversion of CO to CO2 to achieve greater than 75% carbon
capture if only one shift reactor is used.
• The maximum CO conversion in a single shift stage is approximately 75%.
Therefore, the maximum carbon capture possible with only one shift reactor is
also roughly 75%, depending on the separation efficiency of the Selexol unit, and
the initial CO2 content of the syngas (which is a function of the gasifier design).
• The most economic carbon capture design choice is to feed less shift steam
(designing for a S:DG ratio of 0.25, instead of 0.3). Operating with a lower S:DG
ratio impedes the kinetics of CO to CO2 conversion. Consequently, larger and
more costly WGS reactors are required for a similar degree of conversion.
Although a reduction in S:DG ratio requires a larger reactor volume (this analysis
assumed a volume increase of 30%, and subsequently a 30% increase in reactor
cost), the benefit of steam savings – which can then expanded through the steam
turbine to produce additional power – is more than adequate to offset this.

6
 • The only configuration capable of achieving 90% carbon capture (for the arrangement
used in this analysis) is two reactor stages, with a S:DG ratio of 0.3. The maximum
amount of shift steam is required in order to achieve high conversion of CO to CO2,
which will allow for adequate Selexol separation to reach 90% capture.
• Figure 2 indicates that the COE of the single-stage configuration is the same as the two-
stage configuration, for a steam-to-dry gas ratio of 0.25. This result is counterintuitive
since there are fewer shift reactors, and according to Table 1 the steam consumption is
also lower. The single stage configuration is not able to meet the sulfur emission limit
(0.0128 lb SO2/MMBtu), since the WGS catalyst also promotes hydrolysis of carbonyl
sulfide, according to the following reaction:

COS + H2O Æ H2S + CO2 ΔHrxn = -14,526 Btu/lb-mol

Therefore, although only one shift reactor is used, an additional carbonyl sulfide
hydrolysis reactor is also required, which adds additional capital cost.

Figure 3 compares CO2 emissions of an IGCC plant to an uncontrolled, advanced natural gas
combined cycle (NGCC), and also to the emission limits of California’s Senate Bill 1368, which
requires the California Public Utility Commission to "establish a greenhouse gases emission
performance standard for all baseload generation of local publicly owned electric utilities at a
rate of emissions of greenhouse gases that is no higher than the rate of emissions of greenhouse
gases for combined-cycle natural gas baseload generation3." This rate of emissions for a state-
of-the-art NGCC has been established at 1,100 lb CO2/MWh.

An uncontrolled, advanced NGCC has a CO2 emission rate of 800 lb CO2/MWh2, which is
approximately equal to an IGCC plant capturing 60% of carbon emissions. On a cost basis, the
IGCC plant at this emission rate is approximately 42% higher than the NGCC. To meet the
California emission standard of 1,100 lb CO2/MWh, an IGCC plant would use a single shift
stage, with 72% bypass around that reactor and a S:DG ratio of 0.25 to achieve 42% carbon
capture, resulting in a cost of electricity of 9.46 ¢/kWh. The CO2 emissions for an IGCC plant
that did not shift CO, but captured carbon using a Selexol unit, are 1,322 lb CO2/MWh (29%
carbon capture, 9.27 ¢/kWh).

7
 Figure 3 - CO2 Emission Comparison

3.2 Recommendations

For future IGCC designs, it is recommended that the water gas shift step be configured
with larger reactors that are capable of operating with less shift steam. A typical
commercial offering from a catalyst vendor recommends a S:DG ratio of at least 0.3 at
the outlet of the last shift stage. However, discussions with vendors indicated that it may
be possible to purchase reactors designed for a S:DG ratio of 0.25, although this would
increase reactor volume by approximately 30%. It was assumed in this study that capital
cost of the larger shift reactors would also increase by 30%. Therefore, this analysis
explored the tradeoff between reduced shift steam consumption (reduced operating cost)
and increased capital cost for the water gas shift step.

The results in Figure 2 show that for all levels of carbon capture, the cost of electricity is
lowest when less shift steam is used. This trend suggests that although capital cost is
higher due to larger reactors, the savings in shift steam consumption more than offsets
this. For carbon capture below 75%, where a configuration using either one or two shift
stages would be possible, the cost is nearly the same for either option. As explained

8
 above, even though the single stage configuration has one less shift reactor, an additional
COS hydrolysis reactor is required.

The efficiency results in Figure 1 show that when less shift steam is used (S:DG = 0.25),
efficiency is higher, as expected. This is a direct result of more steam being expanded
through the turbine to produce power, instead of being extracted and used for the water
gas shift step. Figure 1 also shows that the efficiency of the two stage, 0.25 S:DG cases
are higher than the single stage, 0.25 S:DG cases, even though the shift steam
consumption is higher. In general, lower shift steam consumption would result in higher
efficiency. When two shift stages are used instead of one, more syngas is bypassed
around the reactor vessels. This leaves more exothermic reaction heat available for
recovery and integration, since there is less mass present (shifted syngas) to absorb it.
Therefore, when possible, it is recommended that two shift stages operating at a steam-to-
dry-gas-ratio of 0.25 (at the reactor outlet) be used for future designs.

4 Base IGCC Case

4.1 Plant Description

The base IGCC plant for this analysis is Case 2 from the reference study2. This case is
based on a 556 MWe (net power output) IGCC plant, using GE Energy gasification
technology, located at a greenfield site in the Midwestern United States. The plant
captures 90% of the carbon in the coal (minus carbon in the slag), and assumes geologic
sequestration. Two pressurized, slurry-fed, entrained-flow gasification trains utilizing
WGS reactors feed two advanced F-Class combustion turbines (rated at 232 MW each).
Two heat recovery steam generators (HRSG’s) and one steam turbine provide additional
power. Carbon dioxide is removed with the two-stage Selexol physical solvent process.
A block flow diagram of the process is shown in Figure 4.

Two gasification trains process a total of 6,005 tons of coal per day. Coal slurry is
transferred from the slurry storage tank to the gasifier with a high-pressure pump. Ninety
five percent purity oxygen is produced in a cryogenic air separation unit for use as the
gasifier oxidant. The coal slurry and O2 react in the gasifier at 815 psia and high
temperature (in excess of 2,400°F) to produce syngas. Hot syngas and molten solids
from the reactor flow downward into a radiant heat exchanger, where the syngas is
cooled to 1,100°F and the ash solidifies. Raw syngas continues downward into a quench
system, where most of the particulate matter is removed, and then into the syngas
scrubber where the remaining entrained solids are separated along with halogens and
ammonia. Slag captured by the quench system is recovered in a slag recovery unit. The
gas is further cooled to accommodate cold cleanup processes, including a carbon bed for
mercury removal.

To achieve the 90% carbon capture goal, a WGS process containing two intercooled sour
shift stages operating at an inlet temperature of 450 oF converts CO to CO2. Carbon
dioxide is removed from the cool, particulate-free gas stream by the Selexol solvent. The

9
 dual-stage Selexol acid gas removal process preferentially removes hydrogen sulfide and
carbon dioxide as purified product streams, which are sent for further processing. The
H2S is converted to elemental sulfur in the Claus plant, and the CO2 is dried and
compressed to 2,215 psia for subsequent pipeline transport. The compressed CO2 is
transported via pipeline to a geologic sequestration field for injection into a saline
aquifer, which is located within 50 miles of the plant.

A Brayton cycle, fueled by the sulfur- and relatively carbon-free syngas, is used in
conjunction with a conventional subcritical steam-based Rankine cycle for combined-
cycle power generation. The two cycles are integrated by generation of steam in the
HRSG, and heat recovery from the IGCC process (radiant syngas cooler). A summary of
plant electrical generation performance is presented in Table 2.

Table 2 - GE IGCC Performance Summary

Gas Turbine Power 464 MW
Steam Turbine Power 275 MW
Sweet Expander Power 6 MW
Auxiliary Power Requirement (189 MW)
Net Power Output 556 MW
Net System Efficiency (HHV) 32.5%
Net Plant Heat Rate (HHV) 10,505 Btu/kWh

4.2 Plant Financial Description

Plant size, fuel type, design and construction time, total plant cost (TPC) basis year, plant
capacity factor, heat rate, fuel cost, book life, and in-service date were used as inputs to
develop capital cost, production cost, and LCOE estimates. Costs for the plant were
based on adjusted vendor-furnished and actual cost data from recent design/build
projects. Values for financial assumptions and a cost summary are shown in Table 3.

Project contingencies were added to each case to cover project uncertainty and the cost of
any additional equipment that could result from detailed design. Process contingency is
intended to compensate for uncertainties arising as a result of the state of technology
development, and also was added to each plant section as appropriate. For more details
on specific process and project contingencies as they were applied to each unit operation,
the report containing the reference case should be consulted2.

The calculated cost of transport, storage, and monitoring for CO2 is $4.20/short ton,
which adds 0.39 ¢/kWh to the LCOE.

Table 3 - Base Case Financial Assumptions

Capacity Factor 80%
Fuel Cost $1.80/MMBtu
Plant Life 30 years
Construction Duration 3 years

10
 Plant in Service January 2010
Capital Charge Factor 17.5%
Total Plant Costiii $2,390/kWe
Levelized Cost of Electricity 10.29 ¢/kWh

iii
Total plant cost includes all equipment (complete with initial chemical and catalyst loadings), materials, labor
(direct and indirect), engineering and construction management, and contingencies (process and project). Owner’s
costs are not included.

11
 Figure 4 - GE IGCC with Carbon Capture

Quench and Gas Cooling

Mercury CO2 CO2 Product
Syngas Shift Reactors BFW Heating Selexol Unit
Removal Compressor
Scrubber and Knockout

Shift Steam

Sour Water
Stripper
Claus Sulfur Product
Plant
Coal
GE Gasifier
Water Recycle to
Coal Slurry Prep

Hydrogenation
Slag Reactor and
Clean Syngas Gas Cooler
Oxidant

Tail Gas Recycle

to Selexol
Elevated Gas Syngas
Vent Gas Nitrogen Diluent
Pressure Turbine Reheater
ASU Combustor and Expander
Stack Gas

Air 2 x F Class Gas Turbines

Flue Gas
HRSG
Main Air Compressor

Turbine Cooling Air

Ambient Air

12
4.3 Base Case WGS Configuration

The water gas shift reaction produces CO2 from CO, so that carbon is converted to a form
that is more readily separated in an acid gas removal process such as a Selexol unit. The
reaction consumes one mol of water per mol of CO converted, and releases heat in the
process:

H2O + CO Æ H2 + CO2 ΔHrxn = -17,697 Btu/lb-mol (1)

The sour water gas shift configuration for the base IGCC case is presented in more detail
in Figure 5, and the corresponding stream data is in Table 4. It should be noted that this
case is from the reference study2, and was specifically developed to capture 90% of
carbon emissions.

The stream data in Table 4 show that the S:DG ratio at the outlet of the final shift reactor
(stream 6) is 0.3. This represents a typical offering from a commercial catalyst vendor.
The function of this excess steam is to drive the shift equilibrium toward the products.

A secondary reaction that occurs on the WGS catalyst is hydrolysis of carbonyl sulfide:

COS + H2O Æ H2S + CO2 ΔHrxn = -14,526 Btu/lb-mol (2)

This reaction converts sulfur to a form (H2S) that is removed more readily than COS in
an acid gas removal system, helping to meet emission specifications. The Selexol
solvent’s affinity for H2S is nearly 4 times greater than it is for COS4. Since this physical
solvent’s driving force is partial pressure, and sulfur concentrations are relatively low to
begin with, conversion to H2S (which the Selexol solvent can separate more easily) is
effective in reducing the size of the Selexol process, while achieving the low sulfur levels
required by local permitting agencies (this analysis assumes 0.0128 lb SO2/MMBtu).

The S:DG ratio used in this base case (0.3) represents a typical offering by a commercial
catalyst vendor. The water gas shift and carbonyl sulfide hydrolysis reactions occur at
locations within the catalyst matrix where water molecules have formed weak chemical
bonds (chemisorption). These locations where the reactions occur are known as active
sites. In order for chemisorption of water molecules to occur on the catalyst surface,
diffusion of H2O through the bulk syngas must first occur. At the base case S:DG ratio,
diffusion rates are fast enough such that there are adequate active catalyst sites on which
the reactions can occur. This helps to maintain reasonable reactor sizes and costs.
Figure 5 - Base Case Water Gas Shift Configuration
2

1 3 4 5 6 7
Raw Shifted
Syngas Syngas

Shift #1 Shift #2

13
 Table 4 - Base Case Water Gas Shift Stream Table
Stream 1 2 3 4 5 6 7
Flow (lb/hr) 1,343,902 239,846 1,583,749 1,583,749 1,583,749 1,583,749 1,583,749
Temperature ( oF) 410 615 446 801 450 519 450
Pressure (psia) 797.7 875.0 797.7 787.7 787.2 777.2 776.7
Enthalpy (MMBtu/hr) -4393.6 -1324.6 -5718.2 -5717.9 -5963.6 -5963.6 -6011.3
H2 mol % 0.26 0. 0.22 0.4 0.4 0.43 0.43
H2O mol % 0.34 1. 0.45 0.27 0.27 0.23 0.23
CO mol % 0.27 0. 0.22 0.04 0.04 0.01 0.01
CO2 mol % 0.12 0. 0.1 0.28 0.28 0.31 0.31
H2S mol % 0.01 0. 0. 0. 0. 0. 0.
CH4 mol % 0. 0. 0. 0. 0. 0. 0.
N2 mol % 0.01 0. 0.01 0.01 0.01 0.01 0.01
Ar mol % 0.01 0. 0.01 0.01 0.01 0.01 0.01
Vapor Fraction 1. 1. 1. 1. 1. 1. 1.

The purpose of this study is to optimize the water gas shift step for lower degrees of
carbon capture (60-90%). The three methods that will be investigated are 1) to bypass a
portion of syngas around the shift reactors, 2) to use less shift steam (a S:DG ratio of 0.25
will be used), and 3) to use one shift reactor instead of two. These will be used in
combination with one another in order to arrive at the optimum configuration for each
level of carbon capture.

5 Alternate Sour WGS Configurations

A simplified process flow diagram of each alternate water gas shift configuration is shown
in Table 5. The technical and economic results of each configuration are shown in the
following sections. The performance of each case was modeled using an AspenPlus 2004.1
simulation of an IGCC plant.

Table 5 - Water Gas Shift Configuration Summary

Case 1 – Single
Shift Stage, S:DG =
0.3

Case 2 – Single
Shift Stage, S:DG =
0.25

14
 Case 3 – Two Shift
Stages, S:DG = 0.3

Case 4 – Two Shift

Stages, S:DG = 0.25

5.1 Case 1 - Single Shift Stage, S:DG = 0.3

Case 1 is characterized by a single shift stage, and fixed S:DG ratio of 0.3 at the reactor
outlet. The bypass is set by the amount of CO conversion needed to meet the carbon
capture goal. The maximum carbon capture possible with this configuration is
approximately 75%. Since there is only one reactor used, the conversion of CO to CO2 is
limited to just over 70%. Given the relatively high CO2 concentration of the syngas
produced by a GE gasifier, 80% of the carbon present is in the form of carbon dioxide
following a single stage of shift. Therefore, assuming a given Selexol performance, this
configuration is capable of converting enough CO to CO2 to achieve 75% capture of
carbon dioxide for an IGCC plant that uses a GE gasifieriv. It is likely that this
configuration will result in a different degree of capture when other gasifiers are used,
since different gasifier models produce syngas streams with varying CO2 levels.
Performance of all other unit operations, including the Selexol process, was kept
constant. Lower carbon capture targets (60-75%) were achieved by bypassing a portion
of the syngas around a single shift reactor.

Figure 6 - Case 1 Water Gas Shift Configuration

Water Gas Shift Reactor COS Hydrolysis

Shift Steam

S:DG = 0.3
Syngas

Syngas Cooling

This configuration requires an additional COS hydrolysis unit in order to achieve an

emission rate of 0.0128 lb SO2/MMBtu. This is due to the syngas being bypassed around

iv
Lower CO to CO2 conversion will result in less overall carbon capture, since the Selexol solvent’s affinity for CO2
is approximately 19 times greater than it is for CO4.

15
 the single shift reactor; the COS present is never hydrolyzed to H2S, and the Selexol
solvent has less of an affinity for COS, resulting in higher total SO2 emissions. This
additional unit operation results in a capital cost increase.

The performance of the Case 1 WGS configuration over the range of carbon capture
goals is shown in Table 6. The plant configuration and financial assumptions are the
same as in the base case, with the exception of the water-gas shift section. The
AspenPlus simulation results indicate that the upper carbon capture limit achievable with
this configuration is 75%, with 6% bypass around the WGS reactor.

Table 6 - Case 1 Performance Results

Carbon Capturev 60% 65% 70% 75%
Syngas Shift Reactor Bypass 37% 26% 16% 6%
Gas Turbine Power (MW) 464 464 464 464
Steam Turbine Power 265 267 268 270
Sweet Gas Expander Power (MW) 6 6 6 6
Auxiliary Load (MW) (177) (179) (181) (183)
Net Power (MW) 558 558 557 556
Net System Efficiency (HHV) 34.3% 33.9% 33.6% 33.3%
Net Plant Heat Rate (Btu/kWh, HHV) 9,956 10,074 10,164 10,255
COE (¢/kWh) 9.78 9.87 9.96 10.05
Total Plant Cost ($/kWe) 2,259 2,280 2,303 2,325

5.2 Case 2 - Single Shift Stage, S:DG = 0.25

The Case 2 configuration (shown in Figure 7) is identical to Case 1, except the shift
steam is reduced such that the S:DG ratio is 0.25. The bypass around the shift reactor
varies in order to achieve the specified degree of carbon capture. This alters the degree
of CO to CO2 conversion in order to achieve the specified carbon capture target. As in
Case 1, an additional carbonyl sulfide hydrolysis reactor is required in order to meet the
sulfur emission limit of 0.0128 lb SO2/MMBtu.

Figure 7 - Case 2 Water Gas Shift Configuration

As stated above, a typical commercial offering from a catalyst vendor requires a S:DG
ratio of 0.3 in order to ensure an adequate number of active sites, keeping reactor size and
cost low. While it may be theoretically possible to reduce this ratio, this will result in an
increase in reactor size and cost. This cost increase represents a tradeoff with respect to

v
All cases assume that the Selexol process removes 93% of the incoming CO2.

16
 capital and operating costs: although capital cost increases due to a larger reactor, less
shift steam will be consumed, lowering operating cost. This steam can then be expanded
in the steam turbine to generate additional power. The Case 2 configuration is an
examination of this tradeoff. The capital cost of the water gas shift island will be higher,
but operating costs will be reduced.

The results for the Case 2 configuration are shown in Table 7. Similar to Case 1, this
configuration is capable of no greater than 75% carbon capture due to the use of only one
reactor. In addition, the low shift steam does not drive the reaction equilibrium toward
the products (H2 and CO2) as aggressively as in Case 1, which had higher steam
consumption.

Table 7 - Case 2 Performance Results

vi
Carbon Capture 60% 65% 70% 75%
Syngas Shift Reactor Bypass 34% 23% 13% 2%
Gas Turbine Power (MW) 464 464 464 464
Steam Turbine Power 270 271 272 275
Sweet Gas Expander Power (MW) 6 6 6 6
Auxiliary Load (MW) 177 179 181 183
Net Power (MW) 562 562 561 561
Net System Efficiency (HHV) 34.5% 34.2% 33.9% 33.6%
Net Plant Heat Rate (Btu/kWh, HHV) 9,899 9,985 10,074 10,164
COE (¢/kWh) 9.74 9.81 9.90 9.97
Total Plant Cost ($/kWe) 2,248 2,269 2,290 2,310

The results in Table 7 show a slight cost and performance advantage for Case 2. This
suggests that although the larger shift reactors result in increased capital cost, this is more
than offset by the savings in shift steam consumption.

5.3 Case 3 - Two Shift Stages, S:DG = 0.3

The Case 3 configuration, shown in Figure 8, is based on a two stage system, with a
portion of the syngas bypassing both stages. It is the same as Case 1, except with a
second stage added. The addition of the second stage will allow for greater CO
conversion, given the same bypass rate and supplemental steam consumption. The
process tradeoff with this configuration is the requirement of an external COS hydrolysis
reactor; although carbon capture is achievable with greater bypass rates, the COS in the
bypass stream is never hydrolyzed in the shift reactors, contributing to greater sulfur
emissions. The supplemental steam flow is regulated such that the steam-to-dry gas ratio
is 0.3 at the outlet of the second shift stage.

vi
All cases assume that the Selexol process removes 93% of the incoming CO2.

17
 Figure 8 - Case 3 Water Gas Shift Configuration

The Case 3 performance results are shown in Table 8. This configuration has the benefit
of being able to accommodate the entire range of carbon capture targets considered in this
study. With high syngas bypass rates, an external COS hydrolysis reactor is required to
achieve the sulfur emission limit of 0.0128 lb SO2/MMBtu. However for the 85% and
90% capture cases, enough hydrolysis occurs directly on the shift catalyst such that the
additional reactor is not required.

Table 8 - Case 3 Performance Results

Carbon Capture 60% 65% 70% 75% 80% 85% 90%
Syngas Bypass 49% 40% 32% 23% 15% 7% 0%
Gas Turbine Power (MW) 464 464 464 464 464 464 464
Steam Turbine Power 267 269 270 272 273 275 275
Sweet Gas Expander Power (MW) 6 6 6 6 6 6 6
Auxiliary Load (MW) (177) (179) (181) (183) (186) (188) (189)
Net Power (MW) 560 560 559 559 558 557 556
Net System Efficiency (HHV) 34.4% 34.1% 33.8% 33.5% 33.2% 32.9% 32.4%
Net Plant Heat Rate (Btu/kWh, HHV) 9,927 10,015 10,104 10,194 10,286 10,380 10,540
COE (¢/kWh) 9.78 9.85 9.94 10.01 10.10 10.17 10.32
Total Plant Cost ($/kWe) 2,259 2,279 2,300 2,320 2,341 2,356 2,390

Comparing the Case 3 results with those from Case 1 shows the cost and performance
differences associated with the addition of a second shift reactor, at an identical steam-to-
dry gas ratio (in this instance, 0.3). Although there is more capital equipment for the
two-stage arrangement, this configuration resulted in higher efficiency, and lower cost.
The addition of the second shift reactor allowed for greater bypass rates to achieve the
same level of capture. Therefore, since there is less syngas mass being shifted, greater
reaction heat recovery is possible between stages (more mass being shifted would result
in an increase in the temperature of the shifted syngas, and less heat available for
recovery). This heat is integrated into the HRSG, allowing for greater steam turbine
power output. A comparison of the Case 3 steam turbine power output to Case 1 (Table
9) shows greater steam cycle power output for all levels of carbon capture.

18
 Table 9 - Steam Cycle Power Comparison
Carbon Capture 60% 65% 70% 75%
Case 1 Steam Cycle Power, MW 265 267 268 270
Case 3 Steam Cycle Power, MW 267 269 270 272

5.4 Case 4 - Two Shift Stages, S:DG = 0.25

The Case 4 configuration, shown in Figure 9, is based on a two stage system, with a
portion of the syngas bypassing both stages. The steam-to-dry gas ratio is reduced in this
case, using the 0.25 S:DG metric. Although this results in larger shift reactors, and
subsequently increased capital cost, a shift steam savings is realized. Similar to Case 3,
this configuration requires an external COS hydrolysis reactor; although carbon capture is
achievable with greater bypass rates, the COS in the bypass stream is never hydrolyzed in
the shift reactors, contributing to greater sulfur emissions.

Figure 9 - Case 4 Water Gas Shift Configuration

The Case 4 performance results are shown in Table 10. This configuration is capable of
meeting the entire range of carbon capture targets, with the exception of the 90% capture
case. This suggests that to achieve 90% carbon capture, not only are two shift stages
required, but high shift steam use is also needed to drive the reaction equilibrium toward
the products (H2 and CO2). With high syngas bypass rates, an external COS hydrolysis
reactor is required to achieve the sulfur emission limit of 0.0128 lb SO2/MMBtu.
However for the 85% capture case, adequate hydrolysis occurs directly on the shift
catalyst such that the additional reactor is not required.

Table 10 - Case 4 Performance Results

Carbon Capture 60% 65% 70% 75% 80% 85%
Syngas Bypass 48% 40% 32% 23% 15% 7%
Gas Turbine Power (MW) 464 464 464 464 464 464
Steam Turbine Power 270 272 274 277 278 281
Sweet Gas Expander Power (MW) 6 6 6 6 6 6
Auxiliary Load (MW) (177) (179) (181) (183) (185) (188)
Net Power (MW) 563 563 563 563 563 563

19
 Net System Efficiency (HHV) 34.5% 34.3% 34.0% 33.7% 33.5% 33.2%
Net Plant Heat Rate (Btu/kWh, HHV) 9,899 9,956 10,044 10,134 10,194 10,286
COE (¢/kWh) 9.75 9.82 9.90 9.97 10.04 10.10
Total Plant Cost ($/kWe) 2,257 2,275 2,294 2,311 2,330 2,342

A comparison of the Case 3 and Case 4 results is presented in Table 11. This shows the
performance changes associated with a reduction in shift steam consumption (from a
steam-to-dry gas ratio of 0.3 in Case 3 to 0.25 in Case 4). Since less shift steam is
consumed in Case 4, steam cycle power increases, and the system efficiency also
increases. As explained earlier, a reduction in shift steam requires larger reactor sizes,
which increases capital cost. Despite this capital cost increase, the savings in shift steam
consumption was great enough to result in a lower levelized cost of electricity. However,
the Case 4 configuration was not capable of achieving enough water gas shift to meet the
90% carbon capture target. This suggests that the incremental shift that allows for
meeting elevated (90% or greater) carbon capture is due to high shift steam consumption
(a steam-to-dry gas ratio of 0.3).

Table 11 - Two Stage Shift Comparison

Case 3 Case 3 Case 4 Steam Case 4 Case 4
Carbon Case 3
Steam Cycle LCOE, Cycle Power, Efficien LCOE,
Capture Efficiency
Power, MW ¢/kWh MW cy ¢/kWh
60% 267 34.4% 9.78 270 34.5% 9.75
65% 269 34.1% 9.85 272 34.3% 9.82
70% 270 33.8% 9.94 274 34.0% 9.90
75% 272 33.5% 10.01 277 33.7% 9.97
80% 273 33.2% 10.10 278 33.5% 10.04
85% 275 32.9% 10.17 281 33.2% 10.10

6 Shift Reactor Design Considerations

6.1 Steam-to-Dry Gas Ratio

The S:DG ratio used in the base case (0.3) represents a typical offering by a commercial
catalyst vendor. The water gas shift and carbonyl sulfide hydrolysis reactions occur at
locations within the catalyst matrix where water molecules have formed weak chemical
bonds (chemisorption). These locations where the reactions occur are known as active sites.
In order for chemisorption of water molecules to occur on the catalyst surface, diffusion of
H2O through the bulk syngas must first occur. At the base case S:DG ratio, syngas water
concentration is high enough to allow for relatively fast diffusion rates. This ease of
diffusion of water through the bulk syngas and onto the catalyst surface results in an
adequate number of active catalyst sites on which the reactions can occur. This helps to
maintain reasonable reactor sizes and costs.

While it is technically possible to achieve comparable levels of CO conversion with less

shift steam, this will require larger reactor sizes. Fewer water molecules in the syngas will
result in slower diffusion of H2O through the bulk syngas, and onto the catalyst surface to

20
form active reaction sites. Therefore, more catalyst surface must be provided to maintain
the same level of CO conversion. This analysis assumes that a reduction in S:DG from 0.3
to 0.25 requires 30% additional reactor volume5, and subsequently 30% cost increase. This
trend is shown graphically in Figure 10.

Figure 10 - Relative Reactor Volume as a Function of Shift Steam

6.2 Water Gas Shift Reactor Pressure Drop

Typical catalyst size for water gas shift service utilizes particles in the range of 3 to 10 mm in
diameter. Since the WGS reactors are typically packed beds, the Ergun equation, shown
below, can be employed to calculate the pressure drop6:

Equation 1 – Ergun Equation for Pressure Drop Through Packed Beds

ΔP ρ f u (1 − ε ) ⎡ (1 − ε ) + 1.75⎤
2

= ⋅ ⋅ ⎢150 ⎥
L gd pφ ε 3 ⎣⎢ φ (Re ) p ⎦⎥
Where

dp = particle diameter
g = gravitational acceleration
L = bed length
ΔP = pressure drop
d p uρ f
(Re) p = particle Reynolds number =
μ
u = superficial fluid velocity

21
 φ = particle shape factor
ε = packed bed voidage
ρf = fluid density
μ = fluid viscosity

Once all the parameters are known, the pressure drop can be calculated from Equation 1.
Since some of the operating conditions of the current WGS reactors have not been selected,
detailed calculations of reactor pressure drop can not be performed. However, relative
pressure drop changes versus the operating S:DG molar ratios can be evaluated easily. Given
the same operating pressure, velocity, and catalyst, the pressure drop is proportional to the
length of the reactor. Given the increase in size (length) due to reduced shift steam
consumption (established in the previous section), the relative pressure drop can also be
calculated. This is shown graphically in Figure 11.

Figure 11 - Relative Reactor Pressure Drop as a Function of Shift Steam

7 Water Gas Shift Background

7.1 Steam Consumption

In order to drive the reaction equilibrium toward the products, an excess of steam is
typically introduced at the shift stage inlet. Depending on the gasifier type (slurry versus
dry feed, or firetube boiler versus syngas water quench) there can be insufficient water
vapor initially present in the syngas, so steam is usually extracted from the steam bottoming
cycle and introduced to the shift process. Therefore, the WGS reaction is usually viewed as
a burden on the net system efficiency, due to steam withdrawal.

22
7.2 Sweet Versus Sour Shift

There are two concepts for shifting coal-derived syngas, a sweet shift and a sour shift, the
difference being the sulfur level in the syngas. The feed to a sweet shift unit must be sulfur
free, due to the poisonous effects of sulfur on the catalyst used for this application. For
coal-derived syngas, sulfur is typically removed by a cold-gas cleaning system such as a
single-stage Selexol unit. The catalyst used for a sour shift is sulfur tolerant, so no
scrubbing is required upstream of the reactor.

Since the WGS reaction is exothermic, a low temperature regime is thermodynamically

favored for driving the reaction toward the products; however, the reaction kinetics favor
high temperature. This competition between thermodynamics and kinetics results in the
reaction being executed in a series of steps, with intercooling between each reactor, to
achieve high CO conversion. The exact number of steps will depend on the degree of
conversion required to achieve the CO2 capture target, as well as the specific catalyst being
used. For IGCC applications where 90% CO2 capture with a cold process (such as Selexol)
is required, typically two (and sometimes three) reactors are used. Table 12 compares
operating temperatures and CO slip for three-stage sweet and sour shifts.

The values in Table 12 show an operating tradeoff between the two shift options: although
a sour shift catalyst is sulfur tolerant, eliminating the capital expenditure associated with
syngas precleaning, it does require lower operating temperatures, which increases
irreversible heat loss in the system. Therefore, the decision that chooses a shift scenario
(sweet versus sour) will balance capital with operating costs.

Table 12 - Sweet and Sour Shift Comparison7

Reactor Temperature, oF CO Slip, mol % (dry)
Sweet Shift Sour Shift Sweet Shift Sour Shift
1st Reactor 662 554 6.41 4.43
2nd Reactor 662 608 2.12 1.77
3rd Reactor 464 608 0.48 0.88

7.2.1 Sweet Shift

The syngas feed to the WGS reactor must be nearly sulfur-free (0.1 ppmv1) for a sweet
shift configuration, requiring an acid gas removal (AGR) system. If a conventional cold
gas cleanup process is used for sulfur removal, the water vapor present in the syngas will
condense during cooling prior to the AGR. Therefore, if a sweet shift is paired with a
cold gas cleanup process (such as Selexol), the syngas feed to the shift reactor will be
nearly moisture-free.

Any water initially present in the syngas that is condensed out due to cooling will have
to be supplemented by steam extracted from the bottoming cycle (to drive the shift
equilibrium), resulting in greater efficiency losses. Therefore, a sweet gas shift may not
be the optimum choice for a syngas stream rich in water vapor, such as that produced
from a slurry-fed gasifier or direct water quench.

23
 A sweet shift may be better paired with a dry fed gasifier, which produces syngas with
lower moisture levels than slurry fed gasifiers. Since there is less moisture present to
begin with, the efficiency loss associated with condensation and subsequent steam
addition would be minimized. Another sweet shift application may be for cogeneration
systems, which produces syngas for power, as well as hydrogen. Since the hydrogen
requires low moisture levels, cold gas cleaning prior to a sweet shift may be an option
for water removal.

7.2.2 Sour Shift

For IGCC applications with carbon capture, a sour shift may be a better fit due to the
sulfur tolerance of the catalyst. An IGCC system that uses a slurry-fed gasifier will
produce syngas with high moisture content. The high water vapor concentration of the
syngas provides a strong partial pressure driving force for the shift equilibrium, with
lesser amounts of supplemental steam required from the bottoming cycle. A sour shift
will promote moisture retention in the vapor phase because there is no upstream cold
sulfur removal required. This would eliminate the need for upstream cold gas cleaning,
and the subsequent water vapor condensation associated with a cold process.

7.3 WGS Reaction Equilibrium and Stage Operation

Water gas shift reactors are generally used in the industrial production of hydrogen, ammonia,
and other bulk chemicals employing synthesis gases. In the catalytic steam reforming of
hydrocarbons, the following general chemical equation applies8:

Cn H m + nH 2O ↔ (n + m / 2)H 2 + nCO (3)

The water-gas shift reaction also occurs in the reformer. In industrial applications the
reforming and shift reactions result in a product with compositions closely approaching
equilibrium. The reformers and the shift converters are fixed bed catalytic reactors. In order to
drive the reaction equilibrium toward the products, excess steam is used. The reactions do not
approach completion in the reformers, usually with 10-15 volume percent CO in the reformer
effluent (dry basis). Further conversion of CO is carried out using water gas shift reactors to
reduce the concentration of CO to about 0.5-1% (5,000-10,000 ppmv). Depending on the
synthesis requirements of the purified syngas, the ratio of CO and H2 is adjusted via the water
gas shift reaction. For example, hydrogen production or ammonia synthesis typically requires
maximum H2 yield. For methanol synthesis, a H2 to CO ratio of 2:1 is required. The water gas
shift reaction can achieve nearly any desired stoichiometry by bypassing part of the total gas
stream and shifting only a portion of it. For IGCC application, the primary objective of the
water gas shift step is to convert CO to CO2 for subsequent removal and sequestration.

The water-gas shift reaction is equilibrium limited and moderately exothermic (-17,697 Btu/lb-
mol). Its equilibrium constant decreases with increases in temperature, therefore high
conversion is favored at low temperature. Low CO levels can only be achieved at low
temperatures or driven thermodynamically by excess steam, even though the kinetics are more
favorable at higher temperatures. Thus, in order to achieve lower equilibrium CO levels, two
or three WGS reactors are typically employed in industry: a high-temperature shift (HTS)

24
reactor, operating between 644oF (340oC) and 986oF (530oC), for rapid CO conversion, and
one or two low-temperature shift (LTS) reactors, operating between 356oF (180oC) to 446oF
(230oC). In commercial applications, adiabatic fixed bed reactors with inter-reactor quenching
are usually used9. The inter-reactor quenching can be accomplished by two ways, direct and
indirect quenching. The indirect cooling makes use of cooling tubes while the direct cooling
employs direct water quench. The direct water quench requires less capital investment but is
less efficient in the recovery of reaction heat.

With a given feed composition, the equilibrium conversion of the WGS reaction can be
determined. It can be verified that for very low exiting CO concentration, either low
temperature, high water content, or some combination of both are required. Under adiabatic
conditions, the conversion in a single bed is thermodynamically limited because the reactor
operating temperature increases as the reaction proceeds. Therefore, to increase conversion,
more than one reactor with intercooling between stages is usually employed. Figure 12 shows
graphically the two-stage WGS adiabatic reactor system with intercooling for syngas
compositions with S:DG molar ratios of 0.3 and 0.25. The figure also shows that the
equilibrium compositions are calculated at the adiabatic exit temperature of the reactors,
consistent with the current AspenPlus simulation program.

Figure 12 - Two Stage WGS Reactor Operation with Intercooling

1

0.9 Stage 2
LT Shift
0.8

Intercooling
0.7
Equilibrium Curve
Steam/DG Ratio = 0.30
CO Conversion

0.6

0.5

Equilibrium Curve
0.4 Stage 1
Steam/DG Ratio = 0.25
HT Shift
0.3

0.2

0.1

0
0 500 1000 1500 2000 2500
o
Temperature, F

7.4 WGS Reaction Kinetics

Although numerous studies of reaction kinetics and mechanisms for the water gas shift reaction
have been reported in the literature, there is still controversy over the reaction mechanism, the
active reaction site, and the effect of pressure10. This disagreement was attributed to the
presence of impurities, the varying degrees of mass transfer limitations, the different types of
catalysts employed, and the fact that most of the experimental reactors operate at or close to
atmospheric pressure.

25
For the HTS catalyst such as iron oxide/chromia, there are two distinctly different kinetic
mechanisms which were proposed: the “adsorptive mechanism” (4) and the “regenerative
mechanism” (5 and 6).

H 2 O + CO → CO( ads ) + H 2 O( ads ) → [int*] → CO2( ads ) + H 2( ads ) → CO2 + H 2 (4)

H 2 O + Re d → H 2 + Ox (5)

CO + Ox → CO 2 + Re d (6)

Red represents a reduced site and Ox, an oxidized site. In the adsorptive mechanism (4), CO
and H2O first adsorb onto the catalyst surface and form an intermediate. Subsequent
desorption results in desorbed hydrogen and CO2. In the regenerative mechanism (5), water
first adsorbs and dissociates on a reduced site of catalyst surface to produce hydrogen and at
the same time, it oxidizes the site. In the following step (6) CO is oxidized to CO2 at this site.

In contrast to rate expressions from detailed reaction mechanisms and rate determining steps,
there are also simple empirical rate expressions proposed which do not consider any
mechanism. Other research groups recognize that the water-gas shift reaction is not a simple
order reaction, especially at higher steam:CO ratios, and have suggested a power-law type of
kinetic equation.

For adiabatic reactors, the rate equation needs to be integrated from the reactor inlet to the
outlet, a very tedious effort only justified for detailed WGS reactor design. For routine design,
it is recommended to evaluate the equilibrium constant, Keq, at the outlet temperature of the
reactor and calculate the rate constant, k, as an arithmetic average of rates at the inlet and outlet
temperatures11.

26
8 References
1
“Optimization of the Shift Conversion Unit in a Gasification Plant,” Rao, A., Verma, A.,
Cortez, D., Presented at the Gasification Technologies Council 2006 Annual Meeting,
Washington, DC, October 1-4, 2006
2
“Cost and Performance Baseline for Fossil Energy Plants – Volume 1: Bituminous Coal and
Natural Gas to Electricity”, August 2007,
http://www.netl.doe.gov/energy-analyses/baseline_studies.html
3
http://www.energy.ca.gov/ghgstandards/index.html
4
“Process Screening Analysis of Alternative Gas Treating and Sulfur Removal for Gasification,”
SFA Pacifi, Inc., Final Report, December 2002
5
Private conversation with commercial catalyst vendor, March 17, 2008
6
“Fluid flow through packed columns,” Ergun S., Chem. Eng. Prog. 48, 89 (1952).
7
“Consider Updates for Gasification Process”, Weishaupt, R., Hydrocarbon Processing, July
2006.
8
Spath, P. L., and Dayton, D. C., Preliminary screening – technical and economic assessment of
synthesis gas to fuels and chemicals with emphasis on the potential for biomass-derived syngas,
Technical Report NREL/TP-510-34929, National Renewable Energy Laboratory, 2003.
9
Cooper¸B. R., and Ellingson, W. A., The Science and Technology of Coal and Coal Utilization,
Plenum Press, New York (1984).
10
“Water Gas Shift Reaction Kinetics and Reactor Modeling for Fuel Cell Grade Hydrogen,’
Choi, Y., and Stenger, H. G., J. Power Sources, 124, 432 (2003).
11
“Design of Water-Gas Shift Reactors,” Moe, J. M., Chem. Eng. Prog., 58(3), 33 (1962).

27